Bis(trialkylphosphine carbon disulfide) nickel compound



United States Patent 3,472,887 BIS(TRIALKYLPHOSPHINE CARBON DISULFIDE)NICKEL COMPOUND Jonathan Turner Carrie], Ridgewood, N.J., and EarleNorman Hewitt, Homestead, Pa., assignors to The International NickelCompany, Inc., New York, N.Y., a corporation of Delaware No Drawing.Filed July 13, 1967, Ser. No. 653,027 Int. Cl. C07f 15/04; A01n 9/36 US.Cl. 260-439 2 Claims ABSTRACT OF THE DISCLOSURE Bis(tertiary phosphine)nickel dicarbonyl compounds are reacted with carbon disulfide byrefluxing the mixture to produce nickel-containing reaction productswhich have utility in the agricultural chemical field. Thenickel-containing reaction product corresponds by elemental analysis to[P(R) 'CS Ni wherein R is an alkyl when bis(trialkylphosphine) nickeldicarbonyl is reacted with carbon disulfide. When bis(triarylphosphine)nickel dicarbonyl is reacted with carbon disulfide, the reaction productcorresponds by elemental analysis to [P(R -CS ]Ni wherein R is a phenyl.

The present invention relates to organo-nickel compounds and thepreparation thereof, and more particularly to the reaction productsobtained by reacting bis(tertiary phosphine) nickel dicarbonyl withcarbon disulfide.

It has now been discovered that a novel composition of matter can beproduced by reacting bis(tertiary phosphine) nickel dicarbonyl withcarbon disulfide.

It is an object of the present invention to provide a process forobtaining a novel composition of matter.

Other objects and advantages will become apparent from the followingdescription.

Generally speaking, the present invention comprises thenickel-containing reaction products of carbon disulfide and a compoundrepresented by the formula wherein R is a substituent selected from thegroup consisting of alkyl groups containing from 1 to about 8 carbonatoms and the phenyl group. The nickel-containing organophosphoruscompounds of the present invention generally correspond to the formula[P(R) -CS Ni wherein R is a substituent selected from the groupconsisting of alkyl groups containing from 1 to about 8 carbon atoms andthe phenyl group and wherein at is a whole integer which is 2 when R isan alkyl and is 1 when R is a phenyl. The compounds of the presentinvention can be prepared by reacting carbon disulfide with abis(tertiary phosphine) nickel dicarbonyl having the general formula[P(R) Ni(CO) wherein R is a substituent selected from the groupconsisting of alkyl groups containing from 1 to about 8 carbon atoms andthe phenyl group by establishing a mixture of the bis(tertiaryphosphine) nickel dicarbonyl and carbon disulfide.

The reaction of carbon disulfide and the bis(tertiary phosphine) nickeldicarbonyl can be conducted at subatmospheric, atmospheric orsuperatmospheric pressures and at temperatures at which the mixture ofthe reactants is liquid. For kinetic reasons, it is advantageous toconduct the reaction at temperatures near the boiling point of thereactant mixture. The kinetics of the reaction can be further increasedby dissolving the reactants in an inert solvent which has a boilingpoint higher than the mixture of the reactants so that the system can beheated to higher temperatures. In order to avoid complex apparatus, thereaction is advantageously conducted at atmospheric pressure and attemperatures near the boiling point of the re- "ice actant mixture. Thebis(tertiary phosphine) nickel dicarbonyl and a stoichiometric excess ofcarbon disulfide are added to a reaction vessel which is provided withmeans for refluxing and the mixture is heated for a suflicient period toassure complete reaction. The excess carbon disulfide is then strippedoff and the nickel-containing reaction product recovered.

When a bis(trialkylphosphine) nickel dicarbonyl is reacted with carbondisulfide, a nickel-containing reaction product which by elementalanalysis corresponds to wherein R is a substituent selected from thegroup consisting of alkyl groups containing from 1 to about 8 carbonatoms is obtained. Although the nickel-containing reaction productscorrespond to aforementioned formula by elemental analyses,ebullioscopic measurements in benzene give values about 3 to 4 times themolecular weight as calculated by the above empirical formula.Furthermore, during the ebullioscopic measurements, the variation of theboiling point of the benzene solution indi cated that intermolecularassociation of one type or another was occurring. Both the departure ofthe predicted values based on the empirical formula from theebullioscopic results and the variation of the boiling point of thebenzene solution during ebullioscopic measurements indicate that thereaction products of bis(trialkylphosphine) nickel dicarbonyl and carbondisulfide are not simple substances. The reaction of abis(triarylphosphine) nickel dicarbonyl with carbon disulfide produces anickel-containing reaction product which by elemental analysiscorresponds to [P(R -CS ]Ni wherein R is a phenyl.

Bis(trialkylphosphine) nickel dicarbonyl compounds such asbis(tributylphosphine) nickel dicarbonyl, bis(trimethylphosphine) nickeldicarbonyl and bis(triethylphosphine) nickel dicarbonyl can be reactedwith carbon disulfide to produce the novel compounds of the presentinvention. Generally, a bis(trialkylphosphine) nickel dicarbonyl can bereadily prepared simply by adding the required amounts of nickeltetracarbonyl to a trialkylphosphine which can be dissolved in a solventsuch as ethyl ether. When gas evolution ceases, the solvent can bevaporized and the bis(trialkylphosphine) nickel dicarbonyl can berecovered. Bis(triphenylphosphine) nickel dicarbonyl can be prepared inthe same manner.

In carrying the invention into practice it is preferred to establish amixture of at least one bis(tertiary phosphine) nickel dicarbonyl havingthe general formula wherein R is a substituent selected from the groupconsisting of alkyl groups containing from 1 to about 8 carbon atoms,and the phenyl group with molar quantities of carbon disulfideequivalent to or in excess of about twice the molar quantity ofbis(tertiary phosphine) nickel dicarbonyl. The mixture is refluxed atatmospheric pressure and at a temperature of from about 42 C. to about48 C. to assure substantially complete reaction. After completion of thereaction any remaining excess carbon disulfide is stripped from themixture by heating to a temperature of about 42 C. to about 48 C. andthe products of reaction are then recovered.

For the purpose of giving those skilled in the art a betterunderstanding of the invention and/or a better appreciation of theadvantages of the invention, the following illustrative examples aregiven:

EXAMPLE I The reaction of a bis(trialkylphosphine) nickel dicarbonylwith carbon disulfide is shown in this example. A mixture of millilitersof nitrogen-purged carbon disulfide, which is equivalent to about 1.65moles, and 0.142

mole bis(tributylphosphine) nickel dicarbonyl was established and wasrefluxed for 16 hours at a temperature of about 42 C. At the end of the16 hour refluxing treatment, the excess carbon disulfide was strippedoff under atmospheric pressure at a temperature which varied betweenabout 42 C. to about 48 C. and was finished under vacuum for 18 hours.

The nickel-containing reaction product analyzed, by weight, 50.0%carbon, 8.6% hydrogen, 9.6% phosphorus, 20.7% sulfur and 10.7% nickelwhich analysis corresponds to the formula [P(C H -CS Ni. Within thebounds of experimental error, the quantitative yield was 100% of thetheoretical amount. The product was a dark brown viscous oil which wasimmiscible in water and miscible in acetone, benzene, chloroform,ethanol, methanol, pentane, dimethoxyethane, diethoxyethane, carbontetrachloride, tetrahydrofuran and toluene.

Ebullioscopic measurements in benzene indicated the molecular weight tobe about 2200 which was observed at the maximum elevation of the boilingof benzene. During the ebullioscopic measurements, indications that sometype of intermolecular associations were taking place were observed.

EXAMPLE II This example confirms that bis(triarylphosphine) nickeldicarbonyl reacts with carbon disulfide in a manner similar tobis(trialkylphosphine) nickel dicarbonyl. A mixture of 0.04 mole ofbis(triphenylphosphine) nickel dicarbonyl and 1.5 moles of carbondisulfide was established. The mixture was refluxed at a temperature ofabout 42 C. for 18 hours. A solid product of reaction was formed and wasextensively washed with carbon disulfide. The solid, nickel-containingreaction product had an elemental composition, by weight, of 57.5%carbon, 3.7% hydrogen, 16.8% sulfur, 7.4% phosphorus and 14.6% nickel,which composition corresponded to the empirical formula Calculationsbased on the empirical formula showed that a yield of about 54.5% hadbeen obtained, i.e., 0.0218 mole or 15.6 grams of the product wereformed. The other product or products of reaction that remained in thefiltrate or in the wash solution appeared to be impuretriphenylphosphine and calculations show that 0.034 mole oftriphenylphosphine was formed.

The character of the nickel-containing product of reaction diiferedmarkedly from the product of reaction obtained in Example I. Forexample, the nickel-containing product of reaction of this example wasinsoluble or difficultly soluble in water, acetone, benzene, chloroform,ethanol, methanol, pentane, dimethoxyethane, diethoxyethane, carbontetrachloride, tetrahydrofuran and toluene. Since this product ofreaction displayed no solubility or very limited solubility in commonsolvents, no ebullioscopic measurements were made to determine itsmolecular weight. Upon heating, this nickel-containing product ofreaction melted at between about 173 C. and about 175 C. withdecomposition.

It is to be observed that the present invention provides a compositionof matter derived by reacting at least one bis(tertiary phosphine)nickel dicarbonyl having the general formula [P(R) Ni(CO) wherein R is asubstituent from the group consisting of alkyl groups containing from 1to about 8 carbon atoms and the phenyl group with an excess of carbondisulfide. The nickel-containing products of reaction appear to bepolymers. The compounds of the prseent invention have utility in theagricultural chemical field, in nematocidal, fungicidal and miticidalapplications.

The invention also provides a process for reacting carbon disulfide anda bis(tertiary phosphine) nickel dicarbonyl compound to formbis(tertiary phosphine carbon disulfide) nickel. The mixture ismaintained at a temperature of about 42 C. and about 48 C. and refluxedto maintain an excess of carbon disulfide. Refluxing is continued untilthe evolution of carbon monoxide ceases.

Although the present invention has been described in conjunction withpreferred embodiments, it is to be unerstood that modifications andvariations may be resorted to without departing from the spirit andscope of the invention, as those skilled in the art will readilyunderstand. Such modifications and variations are considered to bewithin the purview and scope of the invention and appended claims.

We claim:

1. A composition of matter which comprises nickelcontainingorganophosphorus compounds which correspond to the formula [P(R) -CS Niwherein R is an alkyl containing from 1 to about 8 carbon atoms.

2. A composition of matter as described in claim 1 wherein R is an alkylcontaining 4 carbon atoms and the nickel-containing organophosphoruscompound is bis(tributylphosphine carbon disulfide) nickel.

References Cited UNITED STATES PATENTS 3,051,694 8/1962 Meriwether etal. 260-94.l

OTHER REFERENCES Baird et al.: Chemical Communications, No. 2, January1967, pp. 92-4.

TOBIAS E. LEVOW, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R. 260999

